US4547597A - Preparation of halogenated phenols - Google Patents

Preparation of halogenated phenols Download PDF

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Publication number
US4547597A
US4547597A US06/495,382 US49538283A US4547597A US 4547597 A US4547597 A US 4547597A US 49538283 A US49538283 A US 49538283A US 4547597 A US4547597 A US 4547597A
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US
United States
Prior art keywords
process according
complex
phenolic compound
phenol
halogenated
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Expired - Fee Related
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US06/495,382
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English (en)
Inventor
David H. Louks
Leonard R. Thompson
Wayne C. Muench
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Dow Chemical Co
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Dow Chemical Co
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Priority to US06/495,382 priority Critical patent/US4547597A/en
Priority to AU27917/84A priority patent/AU2791784A/en
Priority to BR8402372A priority patent/BR8402372A/pt
Priority to CA000454309A priority patent/CA1217202A/en
Priority to JP59098449A priority patent/JPS59219244A/ja
Priority to EP84106148A priority patent/EP0128458A3/de
Assigned to DOW CHEMICAL COMPANY, THE reassignment DOW CHEMICAL COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: THOMPSON, LEONARD R., LOUKS, DAVID H., MUENCH, WAYNE C.
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/10—Pentachlorophenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to the preparation of halogenated phenolic compounds. More particularly the present invention relates to an improved process for the direct halogenation of phenolic compounds whereby reduced amounts of by-products, particularly halogenated dioxin compounds are also prepared.
  • Halogenated phenols such as chlorinated phenols, especially tetrachlorophenols and pentachlorophenol, are valuable fungicides that are conveniently prepared by the direct halogenation of phenol or halogenated phenols in the presence of various catalysts such as AlCl 3 , FeCl 3 , activated carbon and quinoline, tellurium and various salts thereof, as well as such catalysts in combination with various promoters such as those taught in U.S. Pat. No. 4,376,220.
  • the preferred catalyst is aluminum trichloride.
  • the reaction is conducted neat at a starting temperature of about 65° C.-130° C. After three or four chlorine atoms have been substituted onto the phenol, the temperature of the reaction mixture is increased to maintain a temperature approximately 10° C. above the melting point of the chlorinated mixture. The reaction is normally complete in 5-15 hours. Because the mixture's melting point increases during the later stages of the chlorination, the preparation of pentachlorophenol may require reaction temperatures of up to about 190° C. or even higher so that the reaction mixture remains in a liquid state. It is now known that elevated temperatures necessary for the preparation of highly chlorinated phenols are particularly conducive to the formation of increased amounts of undesirable by-products particularly chlorinated dibenzo-p-dioxins.
  • an improved process for halogenating phenolic compounds comprising:
  • the phenolic compounds suitably halogenated by the present process include any aromatic compound containing phenol functionality that is capable of halogenation and which suitably forms a complex with the complex forming agents employed herein.
  • Preferred are those phenolic compounds meeting the above criteria that are directly halogenated neat only at elevated temperatures.
  • Most preferred are phenol itself as well as partially halogenated derivatives thereof.
  • Especially preferred are phenol and all mono-, di-, tri- or tetrachlorinated phenols or mixtures thereof.
  • halogenating agents suitably employed in the present invention include a halogen compound or a source thereof corresponding to the desired halogen functionality of the resulting product.
  • a preferred halogenating agent is chlorine.
  • the conditions appropriately selected for the halogenation reaction are those previously known in the art.
  • a catalytic amount of a Lewis acid catalyst such as aluminum trichloride or ferric chloride is employed to aid in the reaction.
  • the catalyst is employed in an anhydrous state. Elevated temperatures of from about 50° C. to about 150° C. are employed. Preferred temperatures are those at which formation of appreciable amounts of undesirable halogenated dibenzo-p-dioxins is avoided. Preferred temperatures are from about 80° C. to about 130° C. Most preferred temperatures are from about 90° C. to about 115° C.
  • halogenated dibenzo-p-dioxin compounds is preferably less than about 50 ppm by weight and most preferably less than about 10 ppm based on the weight of the halogenated phenol product.
  • the temperature selected will be determined by the melting point of the reaction mixture keeping in mind that the mixture is desirably maintained in the molten state. Elevated or reduced pressures may be employed as is desired. Preferred pressures are atmospheric or higher.
  • low melting point complexes with the phenolic reactants of the present process is accomplished using any suitable complexing agent. Included are all compounds that are capable of forming stable, isolatable complexes having a melting point less than about 150° C., preferably less than about 130° C. and most preferably less than about 115° C. Identification of suitable complexing agents may be readily determined by the skilled artisan by the simple expedient of combining the phenolic compound and the complexing agent optionally in the presence of a solvent and noting the formation of a stable complex upon isolation thereof. By the term stable is meant that the complex is sufficiently durable so as to exist independently of solvents.
  • Preferred complexing agents according to the present invention are the lower alkyl amide derivatives of lower aliphatic aldehydes, e.g., dimethylformamide, diethylformamide, dimethylacetamide, etc.
  • a particularly preferred complexing agent is dimethylformamide (DMF).
  • DMF dimethylformamide
  • the melting point of the 1:1 complex of DMF and pentachlorophenol has been found to be about 62° C., allowing the neat, direct chlorination of a complex of phenol and DMF to be readily accomplished at temperatures well below 150° C., or even below 130° C. or 115° C.
  • the complex preferably comprises about a stoichiometric amount of the complexing agent chemically bound to the phenolic compound so as to form a stable isolatable species.
  • the product is easily recovered by simply cooling the mixture.
  • the complex may also be recovered by dissolving in organic solvents or by any other suitable method. It has been found that the 1:1 complex of DMF and pentachlorophenol is generally more soluble in commonly employed organic solvents such as methylene chloride than is pentachlorophenol itself.
  • the complex may be employed in applications where previously the halogenated phenol alone has been employed. For example, it has been found that equivalent or even improved fungicidal activity on a weight basis may be obtained by use of a complex of pentachlorophenol and DMF as compared to the use of pentachlorophenol alone.
  • the complex can be easily broken and the complexing agent and halogenated phenol recovered according to well-known chemical techniques.
  • the 1:1 complex of DMF and pentachlorophenol is readily separated by dissolving the same in aqueous base and then neutralizing the base by addition of acid.
  • satisfactory recovery rates may also be obtained by simply contacting the resulting complex with water.
  • the product is analyzed by use of gas phase chromatography employing an internal standard.
  • the phenolic compounds are derivatized with bis(trimethylsilyl)acetamide before injection. Separation is accomplished by a 20-foot, 10 percent UCW 98 column. Determination of dimethylformamide is obtained by a 10-foot column of bonded DEGS on 80/100 Chromasorb W. AW. using an external standard.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US06/495,382 1983-05-17 1983-05-17 Preparation of halogenated phenols Expired - Fee Related US4547597A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US06/495,382 US4547597A (en) 1983-05-17 1983-05-17 Preparation of halogenated phenols
AU27917/84A AU2791784A (en) 1983-05-17 1984-05-11 Preparation of halogenated phenols
BR8402372A BR8402372A (pt) 1983-05-17 1984-05-15 Processo de preparacao de fenois halogenados,novos complexos de fenois e o uso no controle de crescimento microbiano
CA000454309A CA1217202A (en) 1983-05-17 1984-05-15 Preparation of halogenated phenols
JP59098449A JPS59219244A (ja) 1983-05-17 1984-05-16 ハロゲン化フエノ−ル、新規フエノ−ル錯体の製造並びに微生物生育制御における使用
EP84106148A EP0128458A3 (de) 1983-05-17 1984-05-16 Herstellung von chlorierten Phenolen und ihr Gebrauch zum Regeln des Wachstums von Mikroben

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/495,382 US4547597A (en) 1983-05-17 1983-05-17 Preparation of halogenated phenols

Publications (1)

Publication Number Publication Date
US4547597A true US4547597A (en) 1985-10-15

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US06/495,382 Expired - Fee Related US4547597A (en) 1983-05-17 1983-05-17 Preparation of halogenated phenols

Country Status (6)

Country Link
US (1) US4547597A (de)
EP (1) EP0128458A3 (de)
JP (1) JPS59219244A (de)
AU (1) AU2791784A (de)
BR (1) BR8402372A (de)
CA (1) CA1217202A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080061289A1 (en) * 2006-09-08 2008-03-13 Stmicroelectronics S.R.L. Process for synthesizing halogenated derivatives of fluorescein for use in the production of non-volatile memory devices

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0323245D0 (en) * 2003-10-03 2003-11-05 Fujitsu Ltd Soft handover techniques

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131259A (en) * 1937-04-28 1938-09-27 Dow Chemical Co Preparation of pentachloro-phenol
US2440602A (en) * 1943-04-21 1948-04-27 Ici Ltd Manufacture of dichlorophenols
US2494993A (en) * 1943-04-21 1950-01-17 Ici Ltd Manufacture of chlorocresols
US2662918A (en) * 1951-04-18 1953-12-15 Goodrich Co B F Process for the preparation of polychlorinated derivatives of phenol
US3038882A (en) * 1956-12-24 1962-06-12 Richardson Co Method of preparing chlorinated phenolic-formaldehyle condensation products
NL6512570A (de) * 1964-09-29 1966-03-30
US3542882A (en) * 1963-08-30 1970-11-24 Coalite & Chem Products Ltd Chlorinated phenols
US3965158A (en) * 1972-12-29 1976-06-22 Rhone-Progil Process for preparing halophenol sulfonic compounds and halophenols from halobenzene sulfonates
GB1460214A (en) * 1973-11-19 1976-12-31 Rhone Progil Biocidal compositions for the protection of wood
DE2726436A1 (de) * 1976-06-18 1977-12-29 Lankro Chem Ltd Verfahren zur herstellung von p-chlorphenol
DE2632565A1 (de) * 1976-07-20 1978-02-02 Hoechst Ag Umsetzung aromatischer verbindungen mit chlor
US4376220A (en) * 1980-06-09 1983-03-08 Reichhold Chemicals, Incorporated Inhibitor for reducing formation of chlorinated dioxins in manufacture of chlorinated phenols
US4431847A (en) * 1982-07-29 1984-02-14 Ethyl Corporation Method for removing brominated phenolic waste

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3182089A (en) * 1961-01-31 1965-05-04 Nepera Chemical Co Inc Method of preparing 2, 4, 6-triiodinated aromatic compounds

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131259A (en) * 1937-04-28 1938-09-27 Dow Chemical Co Preparation of pentachloro-phenol
US2440602A (en) * 1943-04-21 1948-04-27 Ici Ltd Manufacture of dichlorophenols
US2494993A (en) * 1943-04-21 1950-01-17 Ici Ltd Manufacture of chlorocresols
US2662918A (en) * 1951-04-18 1953-12-15 Goodrich Co B F Process for the preparation of polychlorinated derivatives of phenol
US3038882A (en) * 1956-12-24 1962-06-12 Richardson Co Method of preparing chlorinated phenolic-formaldehyle condensation products
US3542882A (en) * 1963-08-30 1970-11-24 Coalite & Chem Products Ltd Chlorinated phenols
NL6512570A (de) * 1964-09-29 1966-03-30
US3965158A (en) * 1972-12-29 1976-06-22 Rhone-Progil Process for preparing halophenol sulfonic compounds and halophenols from halobenzene sulfonates
GB1460214A (en) * 1973-11-19 1976-12-31 Rhone Progil Biocidal compositions for the protection of wood
DE2726436A1 (de) * 1976-06-18 1977-12-29 Lankro Chem Ltd Verfahren zur herstellung von p-chlorphenol
DE2632565A1 (de) * 1976-07-20 1978-02-02 Hoechst Ag Umsetzung aromatischer verbindungen mit chlor
US4376220A (en) * 1980-06-09 1983-03-08 Reichhold Chemicals, Incorporated Inhibitor for reducing formation of chlorinated dioxins in manufacture of chlorinated phenols
US4431847A (en) * 1982-07-29 1984-02-14 Ethyl Corporation Method for removing brominated phenolic waste

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
M. D. Joesten et al., J.A.C.S., 84, 3817 3821 (1962). *
M. D. Joesten et al., J.A.C.S., 84, 3817-3821 (1962).
R. S. Drago et al., J.A.C.S., 84, 2696 2699 (1962). *
R. S. Drago et al., J.A.C.S., 84, 2696-2699 (1962).

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080061289A1 (en) * 2006-09-08 2008-03-13 Stmicroelectronics S.R.L. Process for synthesizing halogenated derivatives of fluorescein for use in the production of non-volatile memory devices
US7842826B2 (en) * 2006-09-08 2010-11-30 Stmicroelectronics S.R.L. Process for synthesizing halogenated derivatives of fluorescein for use in the production of non-volatile memory devices

Also Published As

Publication number Publication date
AU2791784A (en) 1984-11-22
EP0128458A2 (de) 1984-12-19
BR8402372A (pt) 1984-12-26
CA1217202A (en) 1987-01-27
EP0128458A3 (de) 1986-09-10
JPS59219244A (ja) 1984-12-10

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